Polyamine derivatives

ABSTRACT

New polyamine derivatives of the formula   IN WHICH R, R1, m, n, p and q have the measuring given below in the disclosure and a process for their manufacture. The polyamines are useful as textile plasticisers for synthetic fibres, preferably polyacrylonitrile fibre materials.

United States Patent Kirschnek et al.

POLYAMINE DERIVATIVES Inventors: Helmut Kirschnek, Leverkusen; HansGiirlieh, Cologne, both of Germany Appl No; 331.176

[30] Foreign Application Priority Data Feb. 10. I972 German) 2206302[52] US. Cl. 260/4045; 3/l30.l; 8/l3l; 252/86; 252/88 [5|] Int. Clf C07C103/30 [58] Field of Search 260/4045 [56] References Cited UNITED STATESPATENTS 1055.924 9/]962 Hiestzind 260/4045 3 284.4lb 11/1966 Kumul260/4045 X 3.5 I 7,039 6/l970 Wagner et al. 260/404.5

[451 Nov. 11, 1975 Prinmr E.\'anu'ner-Ethel G. Love Allorney, Agent. orFirm-Plumley 8.: Tyner [57] ABSTRACT New polyamine derivatives of theformula in which R, R, m, n, p and q have the measuring given beldw inthe disclosure and a process for their manufacture. The polyamines areuseful as textile plasticisers for synthetic fibres, preferablypolyacrylonitrile fibre materials.

7 Claims, N0 Drawings POLYAMINE DERIVATIVES The invention relates topolyamine derivates', more particularly it concerns new poly-aminederivatives of the formula 2 The manufacture of the polyaminederivatives according to the invention, of the formula (I), is effectedby reacting acylated polyamines of the formula (co-R) arr-(ca -N-(CH im-(cn NH 2 2; 2n, -+(H) R denotes a C,,C ;,-alkyl radical, preferably a-C -alkyl radical and R denotes the radical of an araliphatic, aromaticor,

preferably, aliphatic monoisocyanate or diisocyanate which is left afterremoving the isocyanate groups,

in is l or 2 and n is 2 or 3, and

p has a value of between L9 and 3.2, preferably 2.4

and 3, with the proviso that the sum p +q has a value between 3 and 4,preferably between 3.2 and 3.9, and the ratio m is I:().ZSU,6,preferably l:U.3-().4, a process for their manufacture and their use astextile plasticisers for synthetic fibres, preferably polyacrylonitrilefibre materials,

For R, C C -alkyl radicals which may be mentioned are the undecyl,tridecyl and pentadeeyl radical and especially C, -C ,-alkyl radicals,such as the heptadecyl, octadecyl, eicosyl and above all the heneicosylradical.

For R the following may be mentioned as examples of radicals whichremain after removal of the isoeyanate groups: the aralkyl radicals,optionally substituted by methyl groups, which remain from araliphaticmonoisocyanates or diisocyanates, such as benzylisocyanate andm-xylylene-diisocyanate, such as the benzyl radical or xylylene radical;the aryl radicals, optionally substituted by halogen atoms orC,-C,-alkyl groups, which remain from aromatic monoisocyanates ordiisocyanates, such as phenylisocyanate, tolylisocyanate,3chlorophenylisocyanate, phenylenel ,4- diisocyanate,toluylene-2,4-diisocyanate, 4,4'-bisisocyanato-diphenylmethane and2,2-bis(4- isocyanatophenyl)-propane, such as the phenyl, tolyl and3-chiorophenyl radical and also arylene radicals, such as thel,4phenylene, 2,4-toluylene, bisphenylenemethane and2.2-bis-phenylenepropane radical; the C -C -alkyl radicals. optionallysubstituted by halogen atoms or C C,-alkoxy groups, which remain fromaliphatic monoisocyanates or diisocyanates, such as methyl-,methoxymethyl-, ethyl-, methoxyethyl-, propyl-, chloropropyl-, butyl-,pentyl-, hexyl-, cyclohexyl-, dodecyland octadecylisocyanate and fromtetramethylene hexamethylene and cyclohexanel ,4- diisocyanate, such asthe methyl, methoxymethyl, ethoxymethyl, ethyl, methoxyethyl, propyl,chloropropyl, butyl, pentyl, hexyl, cyclohexyl, dodecyl and octadecylradical and also the C ,C,, alkylene radicals, such as thetetramethylcne, hexamethylene and L4- cyclohexylene radical, with thetetramethylene, hexamethylene and cyclohexylene radicals as well as theC -a|kyl radicals substituted by C. -C,-alkoxy groups being particularlypreferred R, n and 12 have the meaning indicated under the for mula (l)with isocyanates of the formula tllll in which R and in also have themeaning indicated under the formula (I) under the reaction conditionswhich are in themselves known for the reaction of isocyanates withamines, in such molar ratios that the sum of p q has a value of between3 and 4, preferably 3.2 and 3.9, and the ratio pzq is l:O.25-0.6,preferably l:0.30.4.

The reaction, according to the invention, of the acylated polyamines ofthe formula (ll) with the isocyanates of the formula (Ill) is carriedout, for example, at temperatures of 2()l20C, if appropriate in organicsolvents which are inert towards isocyanate groups, such ashydrocarbons, for example heptane, benzene, toluene or xylene, orhalogenated hydrocarbons, for example tetraehloroethylene orchlorobenzene. If the reaction is carried out in the absence of organicsolvents, temperatures of l00-120C are preferably used; if, on the otherhand, it is carried out in Organic solvents, temperatures of 4()-80Chave proved successful.

The acylated polyamines of the formula (ll) to be used as startingmaterials are in themselves known. They are obtained by acylation ofpolyamines of the formula in which a has the meaning indicated under theformula (I) with carboxylic acids of the formula R-COOH in which R hasthe meaning indicated under the formula (I) or of their derivativescapable of amide formation, such as carboxylic acid halides, especiallycarboxylic acid chlorides, carboxylic acid anhydrides, or lower alkylesters of the carboxylic acids, such as methyl or ethyl esters, in amanner which is in itself known, for example by heating the componentsfor several hours to higher temperatures, for example 140180C, ifappropriate under reduced pressure. The degree of acylation is found bydetermining the acid number (mg of KOH/l g of product) of the reactionmixture.

The polyamine derivatives according to the invention, of the formula(I), are hard waxy products of which the melting point is approximatelybetween 90 and 120C. They are insoluble in water but can nevertheless beconverted into storagestable emulsions, with solids contents of up to 30per cent by weight, in water by means of the known emulsifiers, withoutthe conjoint use of organic solvents and in a simple manner, that is tosay without requiring special mechanical devices such as turbinestirrers, homogenising machines and the like; these emulsions in turndisplay the advantageous property that they can be diluted as desired bysimply pouring into cold or warm water and do not, as is usual, requireprior dissolving under warm conditions.

The polyamine derivatives of the formula (1) according to the inventionare excellent textile plasticisers, especially for textile materials ofsynthetic fibres, such as polyesters, for example cellulose 2/2-acetate, cellulose triacetate, polyethylene terephthalates,polycyclohexanedimethylene terephthalate or polycarbonates; syntheticpolyamides, for example polyhexamethylenediamine adipate,poly-e-caprolactam or poly-w-aminoundecanoic acid and especiallypolyacrylonitrile.

The textile materials can be in the most diverse states of processing,for example in the form of woven fabrics, knitted fabrics, tapes,flocks, fleeces or made-up goods.

The plasticisers according to the invention can be applied both inaccordance with the customary exhaustion processes and in accordancewith the customary impregnating processes, with the polyaminederivatives being used in organic solvents, for exampletetrachloroethylene, or preferably in aqueous emulsions.

The polyamine derivatives according to the invention are advantageouslyemployed in such amounts that the treated textile material displays adeposit of about 0.02-1, preferably 0.2-0.8, per cent by weight ofplasticiser (1).

When using the polyamine derivatives according to the invention in theexhaustionprocess, the textile materials to be finished are agitated inthe treatment baths, for example at temperatures of 30-1l0C, for to 120minutes, using a liquor ratio of l:5l:50. After removing the liquor, thefinished material is dried.

Because of the high stability of salt of the aqueous emulsions of thepolyamine derivatives according to the invention, which remainspreserved even up to near the boiling point of the emulsions, theplasticisers according to the invention can not only be employed in thepost-treatment of dyed materials but also directly in the dye baths(single-bath dyeing-finishing process). This use in dye bathsfurthermore is attractive because the polyamine derivatives according tothe invention, in spite of their high substantivity, show no retardingaction towards cationic dyestuffs. They impair neither the speed ofabsorption nor the exhaustion of the bath of the cationic dyestuffs sothat both deep full colour shades and black dyeings can be produced intheir presence. The high fastness to rinsing of the plasticiser effectsachieved with the compounds according to the invention additionallyfavours the applicability of the products in the single-bathdyeing-finishing process.

Because of their insensitivity towards oxidising agents, such as sodiumchlorite, the plasticisers can also be used in bleaching baths. Sincethey furthermore do not impair the brightening action of cationicwhitening agents, the plasticisation and whitening of grey goods 4 of,for example, polyacrylonitrile can be carried out directly in thebleaching bath with the aid of the compounds according to the invention.

The treatment of the textile materials with the compounds according tothe invention gives the textiles a pleasantly soft slightly greasyhandle. The improved fibre-to-fibre slip achievable by means of thetreatment furthermore results in reduced friction and hence in adistinctly reduced electrostatic charge when using the finished goods.

In the case of articles of texturised polyamide the treatment with thecompounds of the formula (1) according to the invention produces optimumeffects with regard to crease resistance and springy elasticity. Itshould be emphasised that the plasticiser effects achievable not onlydisplay good fastness to rinsing but also a certain resistance towashing towards the mild wet washes which are customary for syntheticfibres. The utility of the textile materials is increased on treatmentwith the compounds according to the invention. For example, knittedgoods of high bulk polyacrylic yarns retain the pleasing wool-likehandle character after repeated mild washes whilst this is not the casewhen using the known plasticisers. The plasticisers according to theinvention display good compatibility with other textile auxiliaries sothat they can, for example, also be combined with other plasticisers.

For emulsifying the polyamine derivatives according to the invention,mixtures of the known cationic and non-ionic emulsifiers areappropriately used, and advantageously a small amount of lower aliphaticcarboxylic acid is also added to the mixtures.

Possible cationic emulsifiers are above all quaternary ammonium,sulphonium or phosphonium compounds, for example N-hexadecylpyridiniumbromide, N-tetradecyl-N-dimethyl-N-benzylammonium chloride, N-stearoylamidopropyl-N-dimethy1-N-B-hydroxyethylammonium phosphate,dodecyltrimethylphosphonium chloride and dodecyldimethylsulphoniumchloride.

Non-ionic emulsifiers which have proved particularly successful arepolyglycol-ether derivatives such as are derived, for example, fromfatty alcohols, fatty acids, fatty amines and alkylphenols. The degreeof ethoxylation of the compounds is advantageously between 6 and 50 molsof ethylene oxide. Ethoxylation products of fatty alcohols arepreferentially employed.

The following may be mentioned as examples of lower aliphatic carboxylicacids: formic acid, acetic acid, propionic acid and glycollic acid.

The manufacture of the stock emulsions from the polyamine derivativesaccording to the invention is advantageously effected by warming 10-30parts of polyamine derivative with 0.2-3 parts of a cationic emulsifierand 0.2-3 parts of a non-ionic emulsifier and also 0.3-5 parts of loweraliphatic carboxylic acid and -90 parts of water to 95C until ahomogeneous mixture has been produced, and then again cooling themixture to room temperature; at times, a further warm ing to 90C may beadvisable.

German Pat. Specification No. 1,201,805 and Belgian Pat. SpecificationNo. 573,541 have already disclosed acylated polyamines as textileplasticisers and French Pat. Specification No. 1,295,047 has alreadydisclosed reaction products of polyamines with fatty acids as textileplasticisers. The polyamine derivatives according to the invention aredistinguished, relative to these known compounds, by betteremulsifiability and by the fact that they yield more wash-resistantplasticiser effects and do not exert any retarding effect on cationicdyestuffs in the dye bath, and that the emulsions manufactured from themdisplay greater stability and improved stability to salt.

EXAMPLE 1 a. 84 g (0.5 mol) of hexamethylenediisocyanate are addeddropwise to the melt of 966 g 1 mol) of the condensation product,described below. of 1 mol of triethylenetetramine and 2.6 mols oftechnical behenic acid. contained under a nitrogen atmosphere in a flaskprovided with a reflux condenser, whilst stirring at 1 1 11 18C. Aftercompletion of the addition of isocyanate the reaction mixture is stirredfor approximately a further minutes at the same temperature and issubsequently cooled.

1,045 g of a light yellow hard waxy reaction product are obtained;solidification point: 1 10-1 12C.

b. The condensation product of triethylenetetramine and technicalbehenic acid employed as the starting compound had been obtained asfollows:

867 g (2.6 mols) of technical behenic acid (average molecular weight:334; mixture of 2% of C-24, 80% of C-22, 12% of C-20, 5% of C-18 and 1%of C-16 fatty acid) were fused in a nitrogen atmopshere. 146 g oftriethylenetetramine 1 mol) were added dropwise to the melt, warmed to180-185C, whilst stirring and distilling off the water of reaction whichforms. Thereafter the reaction mixture was stirred for 2 hours in vacuo(40 mm Hg) at the same temperature and was then cooled to roomtemperature.

Yield: 945 g of a light yellow waxy product; solidification point: 104C;acid number 5.

c. A mixture of 180 g of the polyamine reaction product described undera). 10 g of N-tetradecy1-N.N- dimethyl-N-benzylammonium chloride, 5 g ofthe reaction product of 1 mol of oleyl alcohol with mols of ethyleneoxide, g of glacial acetic acid and 775 g of water is warmed to 95C in astirred apparatus equipped with a reflux condenser, stirred for 30minutes at this temperature, then cooled to C. again warmed to C andagain cooled to room temperature. A mobile, storage-stable emulsion isobtained.

If in Example 1 (a). instead of the fatty acid polyamine condensationproduct used there, 1 mol of the condensation product listed in Column Aof the table which follows is employed. and instead of thehexamethylenediisocyanate used the isocyanate listed in Column B of thetable is employed in the molar amount also indicated in Column B,polyamine reaction products are obtained, the physical properties ofwhich are indicated in Column C and D of the table.

The condensation products listed in Column A, which are characterised bythe fatty acids and polyamines used for their manufacture and by themolar 'amounts employed, were manufactured analogously to Example 1 (b).

The emulsification of the polyamine acylation products obtained waseffected as described in Example 1 (c).

Table A g D Example Condensation product of x mols 2 mols of isocyanateReaction product Appearance 0 of fatty acid and y mols of solidificationpoint polyamine C 2 2.8 stearic acid l methylisocyanate 90-92 lightyellon 1.0 triethylenetetramine hard wax 3 2.6 arachidic acid 1methylisocyanate -102 1 .0 triethylenetetramine 4 1.4 stearic acid 1methylisocyanate 98-100 1.4 behenic acid 1 .0 tripropyleneteiramine 52.8 behenic acid technical l methylisocyanate 1 10-1 12 l .0triethylenetetramine 6 2.7 behenic acid 1 ethylisocyanate 1 10-1 12 1 .0triethylenetetramine 7 3.0 behenic acid 0.8 propylisocyanate l 1 1-1 131.0 triethylenetetramine 8 2.2 behenic acid 1.4 tert.-hutyliso- -1 12 1.0 triethylenetetramine cyan-ate 9 2.5 behenic acid 1.1 hexylisocyanate11 1-113 1 .0 trie thylenetetramine 10 2A behenic acid 0.8 octadecyliso-1 14-1 16 1 .0 triethylenetetramine cyanate 1 1 2.5 helienic acid 1.0ethoxymethyliso- 1 10-1 12 l .0 trie thyleneletramine cyanate 12 2.6behenic acid 1.0 methoxymethy1- 110-1 12 light yellow 1.0triethylenetetramine isocyanate hard was 13 2.6 behenic acid* 1.0methoxy ethyl l 10-1 12 1 .0 triethylenetetramine isocyanate l4 2.7behenic acid 1.0 phenylisocyanate 109-1 1 1 light brown 1.0triethylenetetramine hard wax 15 2.7 behenic acid 0.6 tetramethy1ene-L4-1 12-1 13 light yellow 1.0 triethylenetetramine diisocyanate hard wax 162.5 behenic acid 0.7 hexamethylene-L6- 112-1 13 1 .0 tripropylenetetramine diisocyanate 17 2.6 behenic acid 0.5 pheny1ene-l.4-di-111-112 light broun 1.0 triethylenetetramine isocyanate hard was 18 2.4behenic acid* 0.5 diphenylene-4.4'- 109-1 1 1 1 .0 triethylenetetraminediisocyanate 19 2.5 hehenic acid 0.5 m-xylylenediiso- 1 10-112 1.0tripropylenetetramine cyanate 20 2.6 behenic acid 0.6 cyclohexane-L-l- 112-1 14 light yellow 1.0 triethylenetetramine diisocyanate hard waxtechnical behenic acid. for composition sec Example ltbl.

EXAMPLE 21 Polyacrylonitrile high bulk yam which has been dyed in theusual manner with basic dyestuffs is treated for about minutes at 40C,using a liquor ratio of l140, in a bath which per litre contains 0.7 gof the emulsion described in Example l (c) l8% active substance content)and 0.5 g of 60% strength acetic acid. Thereafter the yarn is freed ofthe treatment liquor by centrifuging and is dried at 60C.

The treated yarn shows a pleasantly soft. slightly greasy handle whichis largely stable to repeated washing at C with a customary finedetergent.

A yarn with an equivalent finish was also obtained if instead of theemulsion according to Example 1 (c) which was used, the same amount ofone of the emulsions according to Example 7 (c), l0 (c), ll (c) or 12(c) was employed.

EXAMPLE 22 Polyacrylonitrile high bulk hank material is introduced,using a liquor ratio of 1:40, into a bath warmed to 80C which per litrecontains 1 g of the basic dyestuff No. l L085 (Colour Index, 3rd.edition), 2.5 g of sodium sulphate, 0.5 g of 60% strength acetic acid,0.25 g of the reaction product of l mol of oleyl alcohol and 50 mols ofethylene oxide and 0,5 g of the emulsion described in Example I (c). Thedye bath is heated to 98C over the course of 30 minutes and is kept atthis temperature for 90 minutes. The bath is cooled to 40C by slowlyrunning in cold water. The goods are then rinsed with cold water,dewatered by centrifuging and finally dried at 60C.

A yarn dyed deep red is obtained which is distinguished by a pleasantsoft handle which is largely resistant to repeated fine washes at 3035Cwith a commercially available fine detergent.

It should be mentioned that during the singlebath dyeing-finishingprocess no flocculation occurs in the dye bath and that the affinity ofthe dyestuff is in no way impaired by the addition of plasticiser.

Emulsions according to Example ll (c), l2 (c), l3 (c) and I6 (c) canalso be used with equal success as the emulsion according to Example 1(c).

EXAMPLE 23 A furnishing fabric weighing 280 g/m", of polyacrylonitrilefibres, is introduced, in the liquor ratio of 1:40, into a bath at roomtemperature which contains, per litre, 1.1 g of the basic dyestuff No. 5l ,005 (Colour index, 2nd. edition), 0.6 g of 60% acetic acid, 0.2 g ofthe reaction product of l mol of oleyl alcohol and 50 mols of ethyleneoxide and 0.5 g of the emulsion described in Example 6 (c). The bath iswarmed to 80C over the course of minutes and to 98C over the course of afurther 60 minutes and is kept at this temperature for 60 minutes. Thedye bath is cooled to about C by running in cold water. The goods arethen rinsed with cold water, largely dewatered by squeezing out andfinally dried at l00C.

The piece goods, dyed dark blue, obtained by the single-bathdyeing-finishing process, are free of creases and breaks and show a verysoft, full handle. This is resistant to repeated washing at 3035C with acommercially available fine detergent.

During dyeing, no flocculation occurs in the dye bath and the affinityof the dyestuff is in no way impaired by the addition of theplasticiser.

8 A fabric with an equivalent finish was also obtained if instead of thepolyamine derivative emulsion according to Example 6 (c which was used,the same amount of one of the emulsions according to Example 5 (c 9 (c),ll (c). 16 (c) or 17 (c) was employed.

EXAMPLE 24 Flocks of polyacrylonitrile fibres are introduced, using aliquor ratio of l:10, into a bath at C which per litre contains 3 g ofthe basic dyestuff No. 48,060 (Colour Index, 2nd. edition), 3 g ofsodium sulphate, [.5 g of 60% strength acetic acid, 0.2 g of thereaction product of 1 mol of oleyl alcohol and 50 mols of ethylene oxideand 0.5 g of the emulsion described in Example l l (c). The bath isheated to a temperature of 98C over the course of 35 minutes and kept atthis temperature for minutes. The bath is then cooled to 45C by runningin cold water. The flocks are then rinsed with cold water, centrifugedto a residual moisture content of 20% and finally dried at a temperatureof 6080C.

A soft flock material dyed in a full yellow is obtained, which showsexcellent spinnability.

In order further to improve the anti-static properties and increase thefibre adhesion, the dyed and treated flock is post-treated at 35C in abath which per litre contains 3 g of dibutylphosphoric acid(diethanolamine salt). The removal of the excess liquor and the dryingof the material takes place as described above.

The pleasantly soft, slightly greasy handle of the flock material is notimpaired by this subsequent anti-static finish.

A material with an equivalent finish is also obtained if instead of thepolyamine derivative emulsion according to Example I l (c) which wasused, the same amount of one of the emulsions according to Example 1(c), 4 (c), 8 (c), 9 (c) or 17 (c) is employed.

EXAMPLE 25 Undyed polyacrylonitrile high bulk hank material isintroduced, in a liquor ratio of 1:40, into a bath at 7075C which perlitre contains 0.35 g of 507z strength sodium chlorite, 0.5 g ofcrystalline oxalic acid, 0.3 g of a chlorite-resistant cationic whitener(for example BLANKOPHOR ACB/Bayer) and 0.5 g of the emulsion describedin Example 15 c. The bath is warmed to 98C over the course of 30-45minutes and is kept at this temperature for 30 minutes. Thereafter thebath is cooled to 40C by running in cold water. The goods are thenrinsed with cold water, dewatered to a residual moisture content of 20%by centrifuging and finally dried at a temperature of 60C.

The high bulk yarn which has in this way been simultaneously bleached,whitened and plasticised shows a high degree of whiteness and apleasantly soft, slightly greasy handle. ln winding and knitting theyarn is further distinguished by excellent processing characteristics.

A material with an equivalent finish was also obtained if instead of thepolyamine derivative emulsion according to Example 15 (c) which wasused, the same amount of one of the emulsions according to Example 3(c), 5 (c), 10 (c), 12 (c), 16 (c) or 20 (c) was employed.

EXAMPLE 26 Knitted goods of texturised poly-e-caprolactam, dyed withdispersion dyestuffs are treated for 20 minutes, using a liquor ratio of1:25, in a bath at 4045C which ted goods thus obtained possess apleasant soft handle and display optimum crease resistance and springyelasticity for this article. The effects achieved are largely resistantto repeated washing at 30-35C with a commercially available finedetergent.

A polyamide knitted fabric with an equivalent finish m was also obtainedif instead of the polyamine derivative emulsion according to Example l2(c) which was used, the same amount of one of the emulsions according toExample9 (c). 11 (c). 15 (c)or l6 (c)was employed. H

We claim:

10 p has a value between L9 and 3.2, with the proviso that the sump +qhas a value between 3 and 4; and the ratio of )1 is 1:0.25-(16.

2. The polyamine derivative of claim 1 in which R is c rcg -illkyl.

3. The polyamine derivative of claim I in which R, is C,C,,,-alkyl;C,C,,,-alkyl substituted by halogen or C,-C,-alkoxy; C -C -alkylene; orcyclohexylene.

4. The polyamine derivative of claim 1 in which R, is tetramethylene,hexamethylene. cyclohexylene or C ,C,, -alkyl substituted by C ,C-alkoxy.

5. The polyamine derivative of claim 2 in which R, is C ,C ,,,-alkyl; C,C,,,-alkyl substituted by halogen or C ,C.,-alkoxy; C C,,-alkylene; orcyclohexylene.

6. The polyamine derivative of claim 2 in which R, is

l. Poly-amine derivative of the formula tetramethylene, hexamethylene.cyclohexylene or (co-R) n air-tca l -u-tcn l -i t-tcu i -tll a l NH COlqM] in which C ,C,,,-alkyl substituted by C ,C,-alkoxy.

R is C,,-C ,,,-alkyl; R, is benzyl; xylylene; phenyl; phenylene. phenylor phenylene substituted with C,-C,-alkyl or halogen;

7. The polyamine derivative of claim 1 in which p has a value between2.4 and 3, with the proviso that the sum p has a value between 3.2 and3.9 and the ratio bis-phenylenemethane; 2,2-bis-phenylene propane; p:qis l:O.3-0.4.

1. POLYAMINE DERIVATIVE OF THE FORMULA
 2. The polyamine derivative ofclaim 1 in which R is C17-C21-alkyl.
 3. The polyamine derivative ofclaim 1 in which R1 is C1-C18-alkyl; C1-C18-alkyl substituted by halogenor C1-C4-alkoxy; C4-C8-alkylene; or cyclohexylene.
 4. The polyaminederivative of claim 1 in which R1 is tetramethylene, hexamethylene,cyclohexylene or C1-C6-alkyl substituted by C1-C4-alkoxy.
 5. Thepolyamine derivative of claim 2 in which R1 is C1-C18-alkyl;C1-C18-alkyl substituted by halogen or C1-C4-alkoxy; C4-C8-alkylene; orcyclohexylene.
 6. The polyamine derivative of claim 2 in which R1 istetramethylene, hexamethylene, cyclohexylene or C1-C18-alkyl substitutedby C1-C4-alkoxy.
 7. The polyamine derivative of claim 1 in which p has avalue between 2.4 and 3, with the proviso that the sum p + q has a valuebetween 3.2 and 3.9 and the ratio p:q is 1:0.3-0.4.